Explosive compositions and method of preparing them



May l2, 1959 A. HYsLoP, .1R 2,886,424

EXPLOSIVE COMPOSITIONS AND METHOD OF' lPREPARING THEM Filed Aug. 4, 1954 2 Sheets-Sheet 2 -Lloum HYDRocARBoN /NMMING cl-AMBERA LIQUID HYDROCARBON LIQUID OXYGEN -LIQUID HYDROCARBON louln OXYGEN IN V EN TOR. ANDREW HYSLOP, JR.

ATTORNEYAv United States Patent C EXPLOSIVE COMPOSITIONS AND METHOD OF PREPARING THEM Andrew Hyslop, Jr., Mount Pleasant, Ohio Application August 4, 1954, Serial No. 447,699 15 Claims. (Cl. 52-1) The present invention relates to explosive compositions and methods of making them; and, more particularly, to explosives using liquid oxygen as the oxidizing agent.

The present application is a continuation-in-part of my copending application S.N. 374,831, entitled Explosive Composition and Method of Preparation, led on August 17, 1953, now abandoned.

Liquid oxygen is now being successfully used in a powerful explosive for blasting in mining operations, especially coal mining. This explosive contains nely divided carbon particles (charcoal, carbon black, and the like) saturated with liquid oxygen. While the carbon particles and the liquid oxygen separately present no hazard in handling or storage, in combination they do, particularly if it is necessary to transport the carbon saturated with liquid oxygen over some distance from a preparation site to the mining areas. Coupled with this disadvantage is the high cost of the carbon arising from its special, and accordingly expensive, mode of preparation.

yLiquid hydrocarbon fuels have been proposed as a relatively low cost substitute for the above-mentioned carbon particles. To the best of my knowledge these have been tried only in liquid or vaporous form in combination with oxygen. The resulting explosives have been too hazardous to use industrially and have accordingly not been generally accepted.

The primary object of my invention is to provide a relatively low cost, industrially practicable explosive composition that is made from liquid oxygen and a liquid hydrocarbon.

Another object of the present invention is to provide a method of making an explosive composition from liquid oxygen and a liquid hydrocarbon. Still another object of my invention is to provide a liqueable or a normally liquid hydrocarbon in a congealed and extrernely subdivided lamentary state.

In accordance with my invention, I have provided a powerful liquid oxygen explosive which used a liquid hydrocarbon as a raw material in a safe but extremely effective manner. I discovered, quite unexpectedly, that a liquid hydrocarbon, when frozen or congealed in an extremely subdivided particulate state, retains its explosivity potential, but is quite safe to handle in combination with liquid oxygen. In its subdivided, particulate state, the normally liquid hydrocarbon can assume two congurations: discrete spherical particles or minute solid filaments can be produced, depending upon the conditions of preparation. So far as I know, no one has ever prepared a frozen hydrocarbon in an extremely subdivided lamentary state let alone observed its unusual behavior with respect to liquid oxygen.

The explosive compositions of my invention may be prepared generally in one of tWo ways. According to the one procedure the explosive composition may be made directly in a single operation. The liquid hydrocarbon, while'in an Vattenuating or particulate state, is

frozen to minute particles or laments in the presence of liquid oxygen. Excess liquid oxygen is used to assure saturation of the frozen hydrocarbon particles or laments and to allow for evaporation of the oxygen before use. The mixture may be prepared at the point of detonation, which actually may be the blast hole itself, or may be prepared offsite and moved to the point of use with impunity.

According to the other procedure, the liquid hydrocarbon is iirst subjected to a freezing temperature while in an attenuating or particulate state to produce extremely line frozen filaments or particles of hydrocarbon. The frozen particulate hydrocarbon is then maintained by suitable refrigeration in this state until it is desired to make the explosive. At that time, the frozen hydrocarbonaceous particles or Vfilaments are saturated with liquid oxygen, and thereupon detonated at the blasting site. Or if the latter is at some distance from the point of preparation of the explosive mixture, excess liquid oxygen may be added to the mixture to allow for evaporation of the oxygen during transportation. The mixture may then be transported with complete safety to the point of use.

For a better understanding of my invention, its other objects and advantages, reference should be had to the following description and accompanying drawings in which:

Figure 1 is a schematic illustration of apparatus for carrying out the preferred embodiment of the invention;

Figures 2 and 3 are enlarged perspective views of nozzles shown in Figure l; Y

Figure 4 is a perspective illustration of an alternate nozzle arrangement;

Figure 5 is a schematic illustration of an alternative apparatus for carrying out the present invention; and

VFigure 6 is a schematic illustration of still another alternative apparatus for carrying out the present invention.

Any normally liquid or liqueiiable hydrocarbonaceous material that will be congealed at liquid oxygen temperature is suitable for use in the explosive compositions of this invention. Such a material serves to supply the necessary combustible for the oxidation reduction reaction. It must be normally liquid or liquetiable in order to permit the formation of the extremely line frozen particles required for the explosive mixture. Accordingly, whether its origin is petroleum, coal tar, shale oil or the like is immaterial. Since one of the objects of my invention is to provide an inexpensive raw material, those liquid hydrocarbons in plentiful supply at low cost are preferred. Included among these are diesel fuels, fuel oils, lubricating oils, gasoline, kerosene, coal tar fractions et cetera. Liquetable solid vcoal tar pitch may be used if desired. Liquid of intermediate viscosity, e.g. from about to 300 Saybolt seconds, are preferred since they lend themselves more readily to dispersion into particles or lilaments of line size. However, the less viscous and the more viscous materials can be appropriately subdivided by proper adjustment of temperature and pressure, as will be described later.

The method of making the congealed particulate hydrocarbon will be described. Referring to Figures 1 to 3 inclusive for the preferred method of congealing the liquid hydrocarbon, a mixing and freezing chamber 10 having vertical side walls and a tapered bottom with a centrally disposed outlet is mounted in an elevated position directly above a receiving container l2. Liquid oxygen from a supply tank 14 is fed through a conduit 16 to a pair of downwardly extending distributing arms 18, fitted with flat spray nozzles 19, shown in perspective in Figure 2. Such nozzles permit a stream of liquid oxygen tov impinge upon a smooth surface 23 to generate asaaeaa a sharp, at fan shaped spray of droplets. The two nozzles 19 are opposed to permit their flat spray discharge to intersect near the central, vertical axis of the mixing chamber 10.

The conduit 16, and the arms 18, preferably are constructed of copper tubing which can be rapidly cooled to permit the flow of oxygen with little ebulition in the conduit. A convenient method for pumping the liquid oxygen from the tank 14 is to provide a cylinder 20 containing pressurized gaseous oxygen which can be throttled through a Valve 21 and a conduit 22 into the sealed liquid oxygen tank 14 above the liquid oxygen layer. The pressure of the oxygen gas above the liquid oxygen in the tank 14 provides a positive liquid oxygen feeding system.

A liquid hydrocarbon is supplied from a tank 25 through a conduit 26 to a pump 27 which develops the desired discharge pressure for the hydrocarbon spray. The pressurized through a conduit 28 under the control of a valve 31 to a spray nozzle 29 which is positioned between the distribution arms 18 of the liquid oxygen supply system. The spray nozzle 29 shown in Figure 3 preferably is 4of the at spray variety although other types of spray discharge are satisfactory. Where a liat spray discharge nozzle is employed to generate the hydrocarbon spray, its discharge preferably is directed vertically along the line of intersection between the two at sprays of liquid oxygen. In contacting the liquid oxygen spray (at 183 C. below zero), the finely divided particles of hydrocarbon liquid are congealed and frozen into a solid form. The freezing is instantaneous so that the solid hydrohydrocarbon from the pump 27 passes' carbon particles have essentially the same shape as the liquid hydrocarbon particles emanating from the spray nozzle 29. The finely divided solid particles of hydrocarbon together with the coalesced liquid oxygen spray pass downwardly through the mixing chamber 10 and are collected in the container 12.

Use of about 6 parts by weight of liquid oxygen for each part of liquid hydrocarbon entering the mixing chamber 10 produces an ebullient mixture of liquid oxygen with finely divided solid hydrocarbons as a dispersed phase in the container 12.

With an excess of liquid oxygen, the freshly prepared mixture in the container 12 is a boiling, cloudy liquid in which the individual particles of solid hydrocarbon are discernible in motion under the agitation of the boiling oxygen. As the liquid oxygen continues to vaporize, the Solid hydrocarbon particles comprise an increasing proportion of the mixture and their movement ceases so that the material becomes a damp, slushy material, like wet snow. As additional oxygen vaporizes, the solid hydrocarbon particles become dry and resemble damp, powdered sugar or cotton candy (depending upon the conditions of formation as will be described later). The solid hydrocarbon particles can be maintained in this state so long as the temperature remains below the congelation temperature of the starting material, even though all of the liquid oxygen has evaporated. Should the dry solid hydrocarbon particles be permitted to rise above their congelation temperature, the original hydrocarbon reappears in its liquid form.

In a preferred spray nozzle for the present invention, three distinct zones occur in the discharge spray. A iiat, atomizing nozzle is shown in Figure 3 to illustrate this phenomenon. On leaving the spray nozzle 29, the liquid forms a at, uninterrupted sheet of continuous liquid. A short distance from the nozzle, discontinuity appears in the liquid sheet and thin, elongated filaments appear. Further attenuation reduces these filaments to fine droplets of liquid. Using a iiat, atomizing nozzle having a spray angle of 80 and an equivalent orifice diameter of 0.043 inch, with a nozzle pressure drop of 350 pounds per square inch, lubricating oils having viscosities of 100 to 300 SSU (100 F.) form a sheet zone in the nozzle discharge extending from the nozzle for a distance of about 3 inches; the lament zone extends for a distance of an additional 3 to 4 inches; and the remainder of the atomizing spray comprises the droplet zone.

I have found that it is possible to produce solidified hydrocarbon particles in filament form by impinging the filament zone of the nozzle discharge against the liquid oxygen spray. `Long, thin, brittle laments of solid hydrocarbons, resulting under these conditions, form a solidified hydrocarbon product which has the appearance of cotton candy. Because substantial interstitial volume exists between the lilarnentary particles, substantial quantities of liquid oxygen can be absorbed by the lamentary material. On the other hand itis possible by suitable vertical adjustment of the nozzle 29 to impinge the droplet zone of the hydrocarbon nozzle discharge into the liquid oxygen spray whereby a solid hydrocarbon material is produced consisting of tiny, rounded solid particles. These particles, when saturated with liquid oxygen, have the appearance of damp, powdered sugar. However, because the interstitial volume is less with these powdery solid hydrocarbons, the oxygenzhydrocarbon ratio in the saturated state is less than that of the lamentary solids. Accordingly, I prefer to prepare my explosive in the ilamentary form.

While the preceding discussion has dealt with the use of spray nozzles for producing tiny particulate masses of liquid hydrocarbons, other apparatus may be employed, for example, tangential spray feeders, or any apparatus which is capable of producing an attenuating stream of liquid particles. For simplicity and convenience, the spray nozzle is preferred. With spray nozzles, accurate control of the lament `zone of the discharge can be maintained.

Suitable ilarnentary material has been prepared from No. l hydraulic oil (a lubricating oil having a viscosity of SSU at 100 F.), for example, which was passed through a spray nozzle under a pressure of 350 pounds per square inch. The oil nozzle discharge at its lament zone impinged against two at sprays of liquid oxygen in the manner illustrated in Figure 1. The resulting lamentary, solid oil had a fluiy, cottony appearance and had a light yellow color, resembling the color of flowers of sulfur. When stirred with a spoon, the cottony mate rial disintegrates to resemble the powdered form, since the delicate, brittle filaments are easily broken.

I have discovered that the nely divided frozen particles of hydrocarbons, when mixed with 2 to 5 times their weight of liquid oxygen, form a powerful explosive which is cheap and easy to prepare, safely and easily handled, and readily subjected to controlled detonation. In its nearly dry form (i.e. low oxygen:hydrocarbon ratio) the solid hydrocarbons will not detonate but will merely burn quietly. Thus the solid hydrocarbon particles are completely safe for handling and transportation in the dry form. While the optimum weight ratio for explosive effectiveness is about 3.5 parts of liquid oxygen to one part of solidified hydrocarbons, nevertheless powerful, elfective detonation can be obtained with the mixture throughout the range of about 1 to l0 parts by weight of liquid oxygen per part by weight of solid hydrocarbon, provided adequate detonating facilities are employed. In the range of about 2 to 5 parts by weight of liquid oxygen per part of solid hydrocarbon, I have been able to obtain detonations merely by heating electrically a thin, bare wire in contact with the mixture. Outside the oxygenzhydrocarbon ratio of 2/ 1 to 5/ 1, but within the ratio range of l/ 1 to 10/ 1, detonation can be obtained consistently by using the detonating caps and fast fuses, such as Primacord.

Accordingly, to prepare an explosive mixture, the dry, solid hydrocarbon particles are mixed with suliicient excess liquid oxygen to assure that the ratio of oxygen to solid hydrocarbon would'be inthe range of about v2/ 1 ticles directly into containers prepared at the drill hole.

In fact where the drilling occurs in geological areas without serious rock ssures, the containers ymay be dispensed with, and the mixture of solid hydrocarbons and liquid oxygen can be discharged directly into the drill hole.

Several alternative procedures for preparing the `finely divided, particulate, frozen hydrocarbon material for use in my new explosive will be described with reference to Figures 4 through 6 inclusive.

f Fig. 4 shows an alternative apparatus for preparing the solid hydrocarbon of the present invention. In Fig. 4 a doughnut-shaped nozzle is provided for feeding liquid oxygen to the mixing chamber. The doughnut-shaped nozzle comprises an annular chamber 50 sealed on all sides, surrounding a central opening 51 through which a spray nozzle 52 for liquid hydrocarbon extends. A conduit 53 communicates with the annular chamber 5t) for introducing liquid oxygen into the chamber. A series of holes 54 is provided along the bottom surface of the annular chamber 56 to discharge liquid oxygen in a curtain around the spray of liquid hydrocarbons. A hollow cone nozzle for the liquid hydrocarbons is ideally suited in this embodiment, although other nozzles may be employed.

In an alternatitve embodiment shown in Fig. 5, a mixing chamber 6i) having vertical side walls and a tapering bottom, is mounted in an elevated position above a collecting container di. A spray nozzle 62 for discharging liquid hydrocarbons is mounted in the bottom of the mixing chamber 60 at the center of a bottom central opening in the tapered section. A liquid oxygen tank 63 is provided above the mixing chamber 60 to permit liquid oxygen to be poured into the chamber 60 ata controlled rate. The liquid oxygen from the tank 63v ows into the tapered bottom section of the chamber 60 around the periphery of the spray nozzle 62. Liquidy hydrocarbon, on discharge from thev spray nozzle 6,2, Vis congealed through the refrigerating action of the liquid oxygen flowing around the nozzle 62, and is collected in the container 61, together with the liquid oxygen. Flow of liquid hydrocarbons and liquid oxygen preferably should commence simultaneously.

Another alternative method of preparing the explosive material of the present invention is illustrated inV Fig. 6. A tank 70 containing liquid oxygen is provided. Liquid hydrocarbons are introduced to a spray nozzle 71 through a conduit 72. A spray of liquid hydrocarbon through the nozzle 71 is initiated outside the tank 70 and thereafter the nozzle '71 is submerged into the liquid oxygen in the tank 70. Satisfactory explosive material having a damp, powdered sugar appearance has been prepared in this,` manner.

lt is also possible to prepare the solidified hydrocarbon in an airborne manner by spraying a finely divided hydrocarbon liquid into a refrigerated chamber maintained at a temperature below the congelation temperature of the liquid hydrocarbon. Satisfactory material has been prepared in this manner by spraying liquid hydrocarbons into a chamber where a freezing temperature was produced by evaporating liquid oxygen fromopen pans in the bottom of the chamber. y

'While liquid oxygen has been described asthe refrigen,

ant material in the above illustrations, nonetheless liquid nitrogen, liquid air, and the likev have been satisfactorily employed to prepare the solid hydrocarbon particles. The properties of the resulting, dry, solid hydrocarbon particles are independent of the refrigerant employed.

For use in explosives, the filaments preferably have an axial diameter of less than 0.001 inch although their length may be as much as 2 inches. When the powdery solid hydrocarbons are used for explosives, the particle diameter is preferably less than 0.01 inch.

` I have further found that it is advantageous in some instances to add finely divided frozen water `particles to `the congealed hydrocarbon in the preparation of my new explosive to reduce its sensitivity. The preferred method for introducing frozen water particles into the mixture is by employing an additional spray nozzle to form a spray of finely divided water particles which impinges against the liquid oxygen sprays along with the hydrocarbon spray. Such a procedure produces a nearly homogeneous mixture of the water particles with the hydrocarbon par ticles. The presence of the frozen water particles changes the form of reaction upon ignition under unconfined conditions from one of detonation to one of deilagration. Nevertheless I have found that a mixture of four parts by Weight of frozen hydrocarbon particles with one part by weight of frozen water particles in sufficient liquid oxygen can be detonated successfully by using fast fuses and detonating caps. When using frozen water as an inhibitor, I prefer to provide frozen water particles in a kquantity up to about one fourth the weight of frozen hydrocarbon; very small quantities of water will exhibit the desired inhibiting effect.

To illustrate the present invention further, a number of examples will be described.

Examplel I Using the apparatus or Fig. l, two flat spray nozzles of the type shown in Fig. 2 were employed for the liquid oxygen spray. These nozzles were nominal 5/6 and 5/32 inch sprays; no distinguishable elect of these two oxygen nozzles was observed in the product frozen hydrocarbon. 'Ihe hydrocarbon material was introduced through a at, atomizing nozzle having an equivalent orifice diameter of 0.043 inch. Satisfactory explosive materials were obtained from the following hydrocarbons:

(a) No. 3 hydraulic oil (lubricating oil having viscosity of 300 SSU at F.) at 55 C. using a nozzle pressure drop of 250 and 600 pounds per square inch.

(b) Diesel fuel oil at 65 F. using nozzle pressure drop of 100 pounds per square inch.

(c) Coal preparation plant spray oil at F., using a nozzle spray pressure drop of 100 and 200 pounds per square inch.

(d) Automotive lubricating oil SAE l0 at 65 F., using a nozzle pressure drop of 100, and `450 pounds per square inch.

(e) No. 1 hydraulic o il at 65 F. using a nozzle pres.- sure drop of 200 and 400 poundsy per square inch.

Example 2 y Using the apparatus shown in Fig. 1 with liquid oxygen being introduced as a spray through two nozzles of the type shown in Fig. 2 having an orice diameter of 56 inch, No. 1 hydraulic oil was frozen in the presence of liquid oxygen spray and discharged from a' flat, ato

izing'nozzle having an equivalent orifice diameter of d of 200 pounds per `tests with this explosive showed no detonation or ignltlon y heated and burned through byan electric current.

explosive material however burned quietlykwithout detof natiOmindicating that the square inch. Heated ball detonation at 1000" F.; detonationshowever occurred when heated balls at 1100 and 1200 F. were lowered into a sample of the product. Example 3 Using the apparatus illustrated in Fig. l, two dat, atomizing nozzles were employed for introducing liquid `oxygen into the mixing chamber. The pressure drop across the oxygen nozzle was l pounds per square inch. No. 1 hydraulic oil was introduced through .a flat, atomizing nozzle at a pressure to introduce a iine stream of liquid water into the mixing chamber concurrently with the No. l hydraulic oil. The

to water was 4 to 1. The water was weight ratio of oil F. and passed through the nozzle at maintained at 40 apressure drop of 450 pounds per square inch. The

resulting explosive mixture was not distinguishable by appearance from the explosive material prepared from No. 1 hydraulic oil alone.

Ony testing the explosives prepared from both oil land water, attempts at detonating the material with hot wires inl the explosive material also resulted in detonaf tion. Hence thecarbontetrachloride was not effective in inhibiting detonation.

Example 5 Using the apparatus of Fig. 1, liquid nitrogen was sprayed into the mixing chamber through two at, atom izing nozzles of the type shown in Fig. 2. No. 3 hydraulic oil was introduced through a at, atomizing nozzle having an equivalent orice diameter of 0.043 inch at a pressure drop of 500 pounds per square inch. The resulting material had an appearance identical to that produced when liquid oxygen was employed as the refrigerant. With the product material saturated in liquid nitrogen, attempts to burn or detonate the saturated hydrocarbons were unsuccessful.

When the liquid nitrogen had boiled away from the solid hydrocarbons, liquid oxygen was added to saturate the solid hydrocarbons. Detonation was obtained with this mixture of liquid oxygen and solid hydrocarbons using Primacord with detonation caps.

Example 6 A batch of cottony explosive material was prepared from No. 3 hydraulic oil using the apparatus shown in Fig. 1. A metal spear, 5 feet long, l inch in diameter, sharpened at one end, was dropped from a height of 10 feet to penetrate containers of the mixture placed over a hole in the ground. Neither explosion nor ignition resulted when the spear was dropped through containers of the material under the following conditions:

(a) The spear was dropped through a one quart cardboard container of the saturated mixture.

(b) The spear was dropped through a metal can lled with four pounds of the saturated mixture.

(c) The spear was dropped through a metal can containing damp (not saturated) mixture.

drop of 600 pounds per square inch. An additional at, atomizing spray nozzle was provided The ratio of No. lv hydraulic oil. to

througha hollow cone, atomizing nozzle having an ori- (d) The metal spear was dropped through a can of dry mixture. y

(e) The metal spear was dropped through a can containing our pounds of the mixture having a substantial excess of the liquid oxygen.

(f) The metal spear` was dropped through a metal can placed on its side vcontaining four pounds of the mixture having an excess of liquid oxygen.

Example 7 Using the apparatus kshown in Fig.

oil at the ambient temperature, 65 F., was frozen in the'presence of liquid oxygen after discharge through a hollow cone, atomizing nozzle having an orifice diameter of 0.0135 inch at apressure drop of 500 pounds per square inch.

Using a hollowcone, atomizing nozzle having an orice diameter of 0.042 inch, a satisfactory explosive material was obtained at pressure drops of 300 and 400 pounds per square inch. Using a hollow cone, atomizing nozzle having an orifice diameter of 0.038 inch, a satisfactory explosive material was obtained at a nozzle pressure drop of 150 pounds per square inch. No. l hydraulic oil was lheated to 120or F. and passed tice diameterof 0.038 inch at a `pressuredrop of`700 pounds per square inch. The saturated product was detonated.

' Example 8 Using the apparatus shown in Fig. 5, No. l hydraulicr oilk was introduced through a hollow cone,y atomizing nozzle having an orifice diameter of 0.042 inch at pressures of 500,v 780, 950, 1100: and 13,50 pounds per square inch. About six parts by weight of liquid oxygen was lpoured into the mixing chamber. The` resulting granular mixture could be detonated in its saturated coni dition. The'weight ratio of liquid oxygen to solid hydrocarbon particles in the saturated condition (Le. no visible liquid oxygen) varied from 2.0 to 2.3, an indication of` the interstitial volume of the solid hydrocarbon.

Example 9 Using the apparatus shown in Fig. 5 and the spray nozzle described in Example 8, a hydrocarbon mixture consisting of 50 parts by weight diesel oil and 50 parts by weight No. 3 hydraulic oil was frozen in the presence of liquid oxygen. The pressure drop across the oil nozzle was 920 pounds per square inch. The resulting material could be detonated.

Example 10 Using the apparatus in Fig. 5 and the nozzle described 1n Example 8, an explosive was prepared by freezing coal preparation plant spray oil in the presence of liquid oxygen. The pressure drop across the oil nozzle was 920 pounds per square inch. Additional explosive cornpositions were prepared from coal preparation plant spray oil discharged through a hollow cone, atomizing nozzle having an orifice diameter of 0.0135 inch at pressure drops of 900 and 1500 pounds per square inch.

Example 11 Using the apparatus shown in Fig. 5 and a hollow cone, atomizing nozzle having an orifice diameter 0.042 inch, various starting materials were prepared into explosives by freezing in the presence of liquid oxygen. Satisfactory explosives were prepared from the following materials:

a) Ordinary gasoline obtained from a convenient lllng station, using a nozzle pressure drop of 900 pounds per square inch.

(b) Diesel fuel oil using a nozzle pressure drop of 900 pounds per square inch. i

4, No. l hydraulic l `satisfactory explosive material.

pressure drop of 900 pounds per square inch.

(d) A viscous wax-oil using a nozzle pressure drop vof 1200 pounds per square inch. This material was too viscous to be pumped through the spray nozzle at the ambient temperature (45 to 55 Fr). Upon a slight heating, however, this material became less viscous, could be pumped through the spray nozzle, and produced a The nozzle pressure drop was 1200 pounds per square inch.

(e) No. 1 hydraulic oil using a nozzle pressure drop of 1200 pounds per square inch.

Example J2 Several ilat pans of liquid oxygen were placed in the bottom of a deep-freeze chest. Metal sheets were placed above each of the pans of liquid oxygen. Ebullition of the liquid oxygen reduced the temperature within the chest to about 120 C. below zero. No. 3 hydraulic oil at 38 C. was sprayed into the chest through a flat, atomizng nozzle having an equivalent orifice diameter of 0.018 inch at a pressure drop of 210 pounds per square inch. The discharge from the atomizing nozzle was congealed in the cold atmosphere within the freezing chest. The light, .congealed particles settled on the flat sheets above the pans containing liquid oxygen and were collected for preparing explosives. The solidied hydrocarbon was indistinguishable in appearance from the hydrocarbon solids prepared by direct impingement of a hydrocarbon spray upon a spray of liquid oxygen. Sample explosives were prepared by mixing the dry, frozen hydrocarbons with liquid oxygen. Using two parts by Weight of liquid oxygen to one part by weight of frozen hydrocarbon, a detonation was obtained by means of Primacord with detonation caps. Using three parts by weight of liquid oxygen to one part by weight of `frozen hydrocarbon a detonation was obtained using adetonation cap alone.

Example 13 An explosive composition was prepared from No. 1 hydraulic oil in the apparatus shown in Fig. 5. The mixing chamber was placed directly above a drilled blasting hole. The resulting explosive dropped directly into the blast hole. The rock around the hole was somewhat cracked from previous blasting in the area. result, considerable stemming of the hole was required, indicating that the explosive owed into the fissures in the rock. One detonating cap was placed at the bottom of the hole and another half way up the hole. The resulting explosion cracked the rock.

A three inch diameter metal downspout tube was inserted into a drill hole and filled with explosive material prepared in the apparatus of Fig. 6, The resulting detonation broke rock well, all the way to the surface. Several large pieces of rock went 6 to 8 feet into the air.

A drill hole seven feet deep, four inches in diameter, was prepared in fairly solid rock. An explosive material was prepared in the apparatus of Fig. 6 and deposited directly into the drill hole. The weight ratio of liquid oxygen to solid hydrocarbons was about 2 to l. On detonation good fragmentation of the rock occurred.

Example J4 An explosive prepared from No. 1 hydraulic oil and liquid oxygen in accordance with Fig. 1 was used to fill 18 cylindrical cardboard containers, each holding about 41/2 pounds of mixture when full. The cartons were lowered into a prepared drill hole 24 feet deep in a limestone ledge. The rst carton was lowered into the hole by means of a length of Primacord tied to it. The top of the hole above the explosive mixture was lled with miscellaneous stemming material, rocks and mud. Detonation was achieved by an electrical blasting cap tied to the Primacord from the hole.

,Similar blasting tests were carried out for `several days Asa` , 1 1 until a total of six drill holes hadv been loaded and blasted in one limestone ledge. Fragmentation of the rock was goo A total of 3300 tons of stone was lifted from the ledge in the six blasts which required a total of 364 pounds of explosives. Thus about 18,100 pounds of stone were prepared from each pound of explosive used. Expressed alternatively about 4.5 cubic yards of solid `stone were fragmented from each pound of explosive. This explosive performance is equivalent to or slightly better than that resulting from the currently employed carbon-and-liquid oxygen explosives. The performance is significantly better than that obtained with the usual xed explosives, such as dynamite.

According to the provisions of the patent statutes, I have explained the principle, preferred construction and mode of operation of my invention and have illustrated and described what I now consider to represent its best embodiment. However, l desire to have it understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specically illustrated and described.

I claim:

1. The method of preparing discrete, lilamentary, solid masses of congealable hydrocarbonaceous substances which comprises forming a spray of discrete, lamentary, liquid masses of said hydrocarbonaceous substances, congealing said spray in a congelation zone maintained at a temperature below the congelation temperature, and recovering discrete, lamentary, solid rmasses of congealed hydrocarbonaceous substances.

2. The method of preparing discrete, lamentary, solid masses of hydrocarbons which are capable of forming discrete, iilamentary, liquid masses on discharge from a spray nozzle, comprising passing said hydrocarbons in liquid form through a spray nozzle, directing the ylilamentary zone of the discharge of said spray nozzle in to a refrigerated zone maintained at a temperature suticiently low to effect congelation of said hydrocarbons and recovering discrete, iilamentary, solidV masses of hydrocarbons at a temperature ibelow the congelation temperature.

3. The method of preparing discrete, tllamentary, solid masses of hydrocarbons which are capable of forming discrete, filamentary liquid masses on discharge from a spray nozzle, comprising passing said hydrocarbons in liquid form through a spray nozzle, impinging the filamentary zone of the discharge upon a spray of liqueed, normally gaseous material maintained at a sutliciently low temperature to effect congelation of said hydrocarbons and recovering discrete, lamentary, solid masses of hydrocarbons at a temperature below the congelation temperature.

4. The method of claim 3 in which the liquefied, normally gaseous material is liquid oxygen.

5. The method of claim 3 in which the liquefied, normally gaseous material is liquid nitrogen.

6. The method of claim 3 in which the liquefied, normally gaseous material is liquid air.

7. An explosive composition comprising discrete, lilamentary, particulate, solid masses of congealable, liquid hydrocarbon, homogeneously interspersed with up to 25 percent by weight of discrete solid particles of water, immersed in quantity of liquid oxygen 2 `to 5 times the weight of the hydrocarbon, said discrete solid particles of water being suicient to reduce the sensitivity of said composition.

8. The method of preparing an explosive material comprising the steps of forming a spray of discrete, liquid masses of hydrocara temperature below the conand saturating said masses with 9. The method of preparing an explosive material comprising the steps of forming a spray of discrete, liquid masses of congealable hydrocarbonaceous materials, passing said spray through a congelation zone maintained at a suciently low temperature to effect congelation, recovering discrete, particulate, solid masses of hydrocarbonaceous substances at a temperature below the congelation temperature, and mixing said masses with 1 to 10 times their weight of liquid oxygen.

10. The method of preparing an explosive material comprising the steps of forming a spray of discrete, liquid masses of congealable hydrocarbonaceous materials, passing said spray through a congelation zone maintained at a suiciently low temperature to eiect congelation, recovering discrete, particulate, solid masses of hydrocarbonaceous, substances at a temperature below the congelationtemperature, and mixing said masses with 2 to 5 times their weight of liquid oxygen. i

l1. The method of preparing an explosive material comprising the steps of passing congealable liquid hydrocarbonaceous material through a spray nozzle, directing the discharge of said spray nozzle into a refrigerated zone maintained at a temperature sufciently low to effect congelation of said hydrocarbons, recovering discrete, particulate, solid masses of hydrocarbon at a temperature below the congelation temperature, and mixing said masses with 2 to 5 times their weight of liquid oxygen.

12. The method of preparing an explosive composition which comprises passing congealable liquid hydrocarbonaceous material through a spray nozzle, impinging the discharge of said spray nozzle upon a ne spray of liquid oxygen, collecting a mixture of discrete, particulate, solid hydrocarbonaceous masses and liquid oxygen from said tine spray, and maintaining 2 to 5 parts by weight of liquid oxygen for each part by weight of solid hydrocarbonaceous masses in said mixture.

13. The method of preparing an explosive material which comprises the steps of passing congealable liquid hydrocarbonaceous material through a spray nozzle, im-

pinging the discharge of said spray nozzle upon a ne spray of liquefied, normally gaseous material, maintained at a temperature suiiciently low to effect congelation of said hydrocarbonaceous material, recovering discrete, particulate, solid masses of hydrocarbonaceous material at a temperature below their congelation temperature, and mixing said masses with 2 to 5 times their weight of liquid oxygen.

14. The method of preparing an explosive composition which comprises forming a spray of congealable liquid hydrocarbonaccous material, forming a second spray of water, impinging both sprays upon a ne spray of liquid oxygen, collecting a mixture of discrete, particulate, solid hydrocarbonaceous masses, solid water masses and liquid oxygen from said fine spray, and maintaining 2 to 5 parts by weight of liquid oxygen for each part by weight of solid hydrocarbonaceous masses in said mixture.

15. The method of preparing an explosive composition which comprises forming a spray of congealable liquid hydrocarbonaceous material, forming a spray of water, impinging both sprays upon a fine spray of 1ique fied, normally gaseous material, maintained at a negative centigrade temperature sufficiently low to elect congelation of said hydrocarbons, recovering discrete, particulate, solid masses of hydrocarbons and Water at a negative centigrade temperature below the congelation temperature of said hydrocarbons, and mixing said masses with 2 to 5 ltimes their weight of liquid oxygen.

References Cited in the le of this patent UNITED STA'TES PATENTS 1,375,243 Weber Apr. 19, 1921 1,508,185 Haynes Sept. 9, 1924 1,627,991 Owen May 10, 1927 2,020,719 Bottoms Nov. 12, 1935 2,444,197 Hampson June 29, 1948 2,745,346 Aitchison et al May l5, 1956 

7. AN EXPLOSIVE COMPOSITION COMPRISING DISCRETE, FILAMENTARY, PARTICULATE, SOLID MASSES OF CONGEALABLE, LIQUID HYDROCARBON, HOMOGENEOUSLY INTERSPERSED WITH UP TO 25 PERCENT BY WEIGHT OF DISCRETE SOLID PARTICLES OF WATER, IMMERSED IN QUANTITY OF LIQUID OXYGEN 2 TO 5 TIMES THE WEIGHT OF THE HYDROCARBON, SAID DISCRETE SOLID PARTICLES OF WATER BEING SUFFICIENT TO REDUCETHE SENSITIVITY OF SAID COMPOSITION. 